Composition and method for producing wrinkle-free permanently pressed cellulosic textile materials

ABSTRACT

A process and a composition useful for imparting abrasion resistance, resistance to frosting, wrinkle resistance, crease retention, wash-and-wear characteristics, durable press characteristics, and permanent press characteristics to cellulosic textile materials and to improve the wet strength, water absorption, and other properties of cellulosic paper. The process comprises; (a) impregnating the textile material or the paper with an aqueous aminoplast system comprising at least one aminoplast and at least one member of a latter recited first group; and (b) curing the aminoplast on the cellulosic material by; (i) irradiation; or (ii) by heating in the presence of an acidic catalyst. The composition comprises an aqueous aminoplast system admixed with an effective amount of a member of a first group consisting of:   WHERE; (A) X IS 0 OR 1; (B) R1 is hydrogen or an alkyl group having about 1-5 carbon atoms; (c) R2 is hydrogen or an alkyl group having about 1-5 carbon atoms; (d) R3 is hydrogen, an alkyl group having about 1-5 carbon atoms, or -SO3 ; (c) R4 is hydrogen, an alkyl group having about 1-8 carbon atoms, CH2CH2OH; or -C6H5; (f) R5 is hydrogen, an alkyl group having about 1-8 carbon atoms, -CH2CH2OH; -C6H5; or -CH2OH; and (g) A is a member selected from a second group consisting of; (i) -NC5H10; (ii) -NC4H8O; and (iii) -NC4H8.

United States Patent 1191 Cicione et al.

[ Dec. 10, 1974 COMPOSITION AND METHOD FOR A PRODUCING WRINKLE-FREE PERMANENTLY PRESSED CELLULOSIC TEXTILE MATERIALS [75] Inventors: Robert J. Cicione, Cranston, R.l.;

Edward G. Najjar,Lincoln; Patricia M. Scanlon, Arlington; John L. Ohlson, Bedford; Joseph F. Finn, Hyde Park, all of Mass.

v [73] Assignee: W. R. Grace Co., New York,

22 Filed: Apr. 20, 1973 21 Appl. No.: 353,161

7 Related U.S. Application Data [62] Division of Ser. No. 195,844, Nov. 4, 1971.

Primary E.ramine rLorenzo B. Hayes Attorney, Agent, or Firm-Elton Fisher; Kenneth Prince v of a first group consisting of: v -i [5 7 ABSTRACT A process and a compositionuseful for imparting abrasion resistance, resistance to frosting, wrinkle resistance, crease retention, wash-and-wear characteristics, durable press characteristics, and permanent press characteristics to cellulosic textile materials and to improve the wet strength, water absorption, and other properties of cellulosic paper. The process comprises; (a) impregnating the textile material or the paper with an aqueous aminoplast system comprising at least one aminoplast and at least one member of a latter recited first group; and (b) curing the amino-" plast on the cellulosic material by; (i) irradiation; or (ii) by heating in the presence of' an acidic catalyst.

The composition comprises an aqueous aminoplast system admixed with an effective amount of a member where; (a) x is O or 1; (b) R is hydrogen or an alkyl group having about l-5 carbon atoms; (c) R is hydrogen or an alkyl group having about 1-5 carbon atoms; (d) R is hydrogen, an alkyl group having about l-5 carbon atoms, or SO;,'; (c) R is hydrogen, an alkyl group having about 1-8 carbon atoms, CH CH OH;' or C H (f) R is hydrogen, an alkyl group having about 18 carbon atoms, CH CH OH; C H or CH OH; and (g) A isa-member selected from'a second group consisting of; (i) -NC =,H (ii) NC,H,,O;

and (iii) --NC H 10 Claims, No Drawings 1 COMPOSITION AND METHOD FOR PRODUCING WRINKLE-FREE PERMANENTLY PRESSED CELLULOSIC TEXTILE MATERIALS This is a division of application $61. No. 195,844, filed Nov. 4, 1971.

BACKGROUND OF THE INVENTION This invention is in the field of cellulosic textile materials and cellulosic paper. More particularly, this invention is in the field of; (a) crease resistant, durable press, or permanent press cellulosic textiles; and (b) cellulosic paper with superior physical properties.

As directed to cellulosic textile materials, this invention is concerned with processes, compositions, and

' agents for treating cellulosic textile materials to render said materials crease resistant,- to make them excellently adapted to receiving and retaining a permanent press, and excellently adapted for use as; (a) wash-andwear and permanent press clothing; and (b) creaser'e- 'sistant and permanent presssheets, pillow cases, curtains, and the like. Cellulosic textile materialswhich have been treated according to this invention have an excellent'band; they also have an abrasion resistance and a tear resistance superior to that of the same cellulosic textile material treated with an aminoplast creaseproofing agent that does not contain a member of the first group recited in the following Summary.

The aqueous aminoplast creaseproofing agent (ACA) of our invention comprises an aqueous solution or an aqueous suspension containing an aminoplast, an acidic catalyst (acidic curing catalyst) for curing the aminoplast, and an effective amount of the first group member recited in said Summary. Said ACA can also contain one or more other additives such'as brighteners, softeners, wetting agents, chelating agents, and the like. Said ACA can be cured by heating or by irradia-,

tion.

Incorporating said first group member into'an ACA causes clothing, sheets, curtains, and the like made from a cellulosic textile material which has been impregnated with said ACA, dried, and cured to have a far better hand, a greater abrasion resistance, a greater crease recovery, a greater tensile strength, an excellent shrink resistance, and less frosting than clothing,

sheets, curtains, and the like made from the same lot of sheets, curtains, and the like made from the same lot of cellulosic textile material which has been treated with the AAC which has not had an effective amount of said first group member incorporated therein.

The reason for these unexpected beneficial results is not understood especially since Frick, et. al., US. Pat.

No. 3,144,299 (8/1 16.3) teach that a finishing agent for cellulosic textile material must have 2 or more methylol groups per molecule and we have found that no member of said first group has more than one methylol group per molecule and many members of said first group do not contain a methylol group.

Prior art methods and prior art systems for treating cellulosic textile materials to make said mateifials crease resistant and to give them durable press and permanent press characteristics are well known to those skilled in the art. Among the many references which teach methods and systems useful for this purpose are the following US. Pats.:

Theuse of aqueous aminoplast systems to improve the physical properties of paper is also well known to those skilled in the art. Where used to treat cellulosic paper, an ACA is often called an aqueous aminoplast paper treating agent aterminology which we have adopted and which we use in our claims. Whereused to treat cellulosic paper an AAC is often called an aqueous aminoplast paper treating composition a terminology which we have adopted and which we use in our claims.

The ACA, AAC, aqueous aminoplast paper treating agent, and aqueous aminoplast paper treating composition of this invention can contain up to about or more of at least one water soluble non-aqueous solvent such as dioxane, methyl alcohol, ethyl alcohol, isoprocellulosic textile material treated with the ACA which invention comprises an aqueous solution or aqueous suspension containing an aminoplast and an effective amount of the first group member recited in said Summary. Said AAC can also contain'one or more other additives such as brighteners, softeners, wetting agents, chelating agents, and the like, but said AAC is substantially free of acidic curing catalyst (acidic catalyst). Said AAC can be cured by irradiation or by heating in the presence of an acidic catalyst (e.g., S0 I-ICl, I-IBr, or the like).

Incorporating said first groupmember into an AAC causes clothing, sheets, curtains, and the like made from a cellulosic textile material which has been impregnated with said AAC, dried, and'cured to have a far better hand, a greater abrasion resistance, a better crease recovery, a greater tensile strength, an excellent pyl alcohol, propyl alcohol, dimethylformamide, dimethyl sulfoxide, and the like.

The process, ACA, and AAC of our invention are useful for preparing permanent press, creaseproof, and wash-and-wear clothing and for preparing permanent press and creaseproof fabric for use in making articles such as pillow cases, bed sheets, tablecloths, drapes, window curtains, and the like.

This invention is also in the field of cellulosic paper and-the treatment of said paper with aqueous aminoplast systems (which can contain up to about 50% or more of at least one non-aqueous solvent such as dioxane, methyl alcohol, dimethylforrnamide, dimethylsulfoxide, propyl alcohol, ethyl alcohol, and the like) to improve the papers properties especially its wet strength and water absorbence.

The treated paper is especially useful as paper toweling, wet strength wrapping paper, and the like.

Where using an aqueous aminoplast composition (AAC) to treat paper, the composition is often called an aqueous aminoplast paper treating composition a terminology which we use in our claims.

Where using an aqueous aminoplast creaseproofing agent (ACA) to treat paper, the agent is often called an aqueous aminoplast paper treating agent a terminology which we use in our claims.

Objects of this invention include providing; (a)

agents, compositions, and processes useful for preparing crease resistant, wash-and-wear, permanent press, and durable press cellulosic textile fabrics having a high abrasion resistance, excellent wrinkle resistance, excellent dimension stability, high tear resistance, excellent tensile strength, substantial freedom from frosting, and an excellent hand; and (b) agents, compositions, and processes for preparing paper with superior physical properties. Still other objects will be readily apparent to those skilled in the art.

SUMMARY OF THE INVENTION In summary, this invention is directed to a composition' of matter (an improved aqueous aminoplast creaseproofing agent (ACA) of our invention) prepared by admixing an aqueous aminoplast creaseproofing agent and an effective quantity of a member selected from a first group consisting of;

f. R, is hydrogen, an alkyl group having about l-8 carbon atoms, CH CH OH';

g. A is a member selected from a second group consisting of;

the ACA containing an effective amount (or quantity of aminoplast.

DESCRIPTION OF PREFERRED EMBODIMENTS In preferred embodiments of the composition set forth in the above Summary:

1. x is O; R is 'CH3; and R R R and R are hydrogen.

2. x is 0; R is CH;,; R is hydrogen; R is SO;{:

R is H; and R is H or CI-I OI-I. I

3. x is 0; R is CH R R and R are hydrogen; and R is CI-I OH.

This invention is also directed to:

l. A composition consisting essentially of a cellulosic textile material wetted with about 10 of the composition of the above Summary. I

I 2. A composition consisting essentially of a cellulosic textile material wetted with about 10 100% of the composition of the above Summary and then dried.

3. A composition'consisting essentially of a cellulo'sic textile material wetted with about 10 100% of the composition of the above Summary, dried, and then cured by; (a) heating; or (b) irradiating (e.g.,

with infrared, ultraviolet, gamma rays, X-rays, an electron beam, a neutron beam, or a proton beam).

where;

a. x is 0 or 1;

b. R is hydrogen or carbon atoms;

c. R is hydrogen or an alkyl group having about l-5 carbon atoms;

(1. R is hydrogen, an alkyl group having about l-5 carbon atoms, or SO{;

e. R, is hydrogen, an alkyl group having about l-8 carbon atoms, -CH CH OH; or.

an alkyl group having about l-5 f. is hydrogen, an alkyl group having about 1 8 carbon atoms, -CH-,CH ()H;

or -CH OH; and l I g. A is a member selected from a second group consisting of;

' the AAC containing an effective amount (or quantity) of aminoplast. In especially preferred embodiments of the composition set forth in Embodiment A, supra;

l. x is R is CH and R R R4, and R are hydrogen.

2.): is 0; R is CH;;; R is hydrogen; R is --SO{; R is H; and R is H or -CH OH. 3. x is 0; R is ---CH;,; R and R are hydrogen and R is CH OH.

This invention is also directed to:

l. A composition consisting essentially of a cellulosic textile materialwetted with about 100% of the composition of Embodiment A, supra.

2. A composition consisting essentially of a cellulosic textile material wetted with about 10 100% of the composition of Embodiment A, supra, and then dried.

3. A composition consisting essentially of a cellulosic textile material wetted with about 10 100% of the composition of Embodiment A, supra, dried, and

then cured by;-(a) irradiating (e.g., with infrared,

ultraviolet, or high energy radiation such X-rays, gamma rays, an electron beam, a proton beam, or a neutron beam); or (b) by heating in the presence of an acid catalyst (e.g., HCl, HBr, S0 formic acid vapor, and the like).

In another preferred embodiment (Embodiment B) this invention is directed to a composition prepared by impregnating a cellulosic textile material with an effective amount (e.g., preferably about 25 100%) of an aqueous solution of a member selected from a first group consisting of;

b. R, is, hydrogen or an alkyl group having about l-5 carbon atoms;

c. R is hydrogen or an alkyl group having about l-5 carbon atoms;

d. R is hydrogen, an alkyl group having about l-5 carbon atoms, or .SO{;

e. R, is hydrogen, an alkyl group having about l8 carbon atoms, --CH CH OH; or

f. R hydrogen, an alkyl group having about 1 'carbon atoms, CH2CH2OH',

or -CH OH; and

of the aminoplast.

In especially preferred embodiments of the composition setforth in Embodiment B, supra:

1. x is 0; R is -CH and R R R and R are hydrogen.

2. x is O; R is CH R is hydrogen; R is -SO R is H; and R is H or CH OH.

3. x is 0; R is CH R R and R are hydrogen;

and R is CH OH.

4. The composition is dried.

5. The dried composition (the composition of item 4,

supra) is cured with'formaldehyde (e.g., by heating in the presence of HCHO and an effective quantity of a gaseous acidic catalyst (e.g., HCl, l-IBr, HI, S0 formic acid vapor, or the like) or by irradiating (e.g., with infrared, ultraviolet, X-rays, gamma rays, an electron beam, a neutron beam, or a proton beam) in the presence of HCHO). The formaldehyde can be conveniently supplied by vaporizing formaldehyde from an aqueous formaldehyde solution, by heating paraformaldehyde or by heating trioxane preferably in the presence of a catalyst such as BFg or other cationic catalyst (Lewis acid).

In another preferred embodiment (Embodiment C) this invention is directed to an improvement in a process for manufacturing a garment from a fabric prepared from a cellulosic textile material comprising impregnating the fabric with a heat curable aqueous aminoplast creaseproofing agent (ACA), said heat curable aqueous aminoplast creaseproofing agent consisting essentially of; (a) water; (b) an aminoplast; and(c) an acidic catalyst. Said aminoplast creaseproofing agent (actually the aminoplast component of said agent) is also radiation curable (e.g., it can be cured by irradiation with gamma rays, X-rays, ultraviolet radiation,

infra radiation, a neutron beam, a proton beam, or an electon beam). Curing said agent with radiation is fully equivalent to curing it with heat and is encompassed herein. Where curing by radiation, the presenceof the acidic catalyst (acidic curing catalyst) does no'harm ,but neither does it (the acidic curing catalyst) serve any useful. purpose. Hence, said catalyst need not be present where curing by radiation. However, said catalystv is required where curing by heating. Curing by radiation in the presence or absence of said catalyst is fully equivalent to curing ,with heat in the presence of said catalyst.

nated, dried, completed, and creased garment is cured by radiation, or it is heated (e.g., to about 120 205C. preferably about 150 200C), to cure the aminoplast and insolubilize it in situ so that the completed garment is pressfree and the imparted creases therein are unaffected after repeated washing of the garment, the-improvement comprising incorporating into (i.e., admixing with) the heat curable aminoplast R is H; and R is H or CH OH. 3. x is R is --CH:,; R ,-R and R are hydrogen;

and R5 iS In another preferred embodiment (Embodiment D-) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast composition (AAC) an aqueous aminoplast system which issubstantially free of acidic curing catalyst and which can contain a softener, a

brightener, a wetting agent, a chelating agent, and the like. The process comprises impregnating the cellulosic textile material with the AAC, drying the impregnated cellulosic textile material and curing the aminoplast thereon by maintaining the dried impregnated cellulosic material in the presence of a gaseous acidic cata creaseproofing agent an effective amount (or quantity) I of a member selected from a first group consisting of;

where;

a.xisOor 1;

b. R, is hydrogen or an alkyl group having about l-5 carbon atoms;

c. R is hydrogen or an alkyl group having about l-5 carbon atoms;

d. R is hydrogen, an alkyl group having about l-5 carbon atoms, or SO{; e. R, is hydrogen, an-alkyl group having about l-8 carbon atoms, CH CH OH orv f. R is hydrogen, an alkyl group having about l8 carbon atoms, -CH CH OH',

g. A is. a member selectedfrom a second group sisting of;

lyst such as a hydrogen halide, S0 or formic acid vapor at a temperature above about 25C. (preferably at about 50-65C. for about'Vz to 60 minutes) or by irradiating the dried impregnated cellulosic textile material with infrared, ultraviolet, 'X-rays, gamma rays, a proton beam, a neutron beam, or an electron beam; the improvement comprises incorporating into (i.e., admixing with the AAC an effective amount (or an effective quantity) of a member selected from a first group consisting of; v

R: o R; 2 R CH N/ 1 \l/x \-,andR1I om/ dA where;

a. x is O or 1', b. R is hydrogen or an alkyl group having about 1-5 carbon atoms; c. R is hydrogen or an alkyl group having about l-5 carbon atoms; i d. R is hydrogen, an alkyl group having about 15 carbon atoms, or SO{; e. R is hydrogen, an alkyl group having about l-8 carbon atoms, CH CH OH; or

' f. R is hydrogen, an alkyl group having about l-8 carbon atoms, CH Ch OH; v

or -CH OH; and g. A is a member selected from a second group consisting of;

(l) orncm --N CH1 cm-om (ii) CH2CH2 N \crn-cn/ and (m) cn,-on,

orb-cm the AAC, after admixing with the first group member, containing an effective amount of the aminoplast. (See U.S. Pat. No. 3,518,044, Reinhardt, et al., 8/129 and US. Pat. No. 3,450,485, Reinhardt, et al., 8/1 16.3)

' 1n the process of Embodiment D, supra:

l. x is R is -Cl-l and R R R and R are hydrogen. 2. x is 0; R is -CH R is hydrogen; R is SO{;

R is H; and R is H or CH OH. 3. x is 0; R is CH R R and R are hydrogen;

and R, is CH OH.

In another preferred embodiment (Embodiment I E") this invention is directed to an improvement in a process for rendering a cellulosic textile material creaseproof by contacting said textile material with a gaseous aldehyde (e.g., formaldehyde, glyoxal, acrolein, and their homologs, see US. Pat. No. 3,528,762, Lauchener, 8/116) and a gaseous acidic catalyst, the improvement comprising impregnating said textile material with a sufficient quantity of an aqueous solution of a member selected from a later recited first group to provide an effective amount of the first group member before contacting the cellulosic textile material with the aldehyde and the gaseous acidic catalyst, the first group consisting of;

b. R is hydrogen or an alkyl group having about 1-5 carbon atoms;

c. R is hydrogen or an alkyl group having about 1-5 f. R is hydrogen, an alkyl group having about 1-8 carbon atoms, -CH CH OH;

or CH OH; and g. A is a member selected from a second group consisting of;

10 the aqueous solution of the first group member contains' about 1 4 40% (preferably about 5 20%) of the first group member. The aqueous solution of the first group member can contain a wetting agent, a chelating agent, a brightener (i.e., a textile brightener or brightening agent) and a softener (i.e., a textile softener or softening agent). Since the brightener and/or softener can be only slightly soluble (or substantially insoluble) in water it is readily apparent that the aqueous'solution of the first group member can actually be an aqueous dispersion of undissolved brightener or softener with the first group member dissolved in the aqueous phase.

1 This process has also been used to improve the physical 2. x is 0; R is drogen. 3. x is 0; R is CH ;R is hydrogen; R is SO;, R is H; and R is H or ,Cl-l Ol-l. 4. x is 0; R is -CH R R and R are hydrogen;

and R is CH OH.

CH and R R R and R are hyln another preferred embodiment (Embodiment- F) this invention is directedto an improvement in a process for treating a cellulosic textile material with 'an aqueous aminoplast creaseproofing agent (ACA) an aqueous aminoplast system which contains an effective amount of an acidic curing catalyst and which can contain a softener, a brightener, a wetting agent, a chelating agent, and the like. The process comprises impregnating the cellulosic textile material with the ACA, drying the impregnated cellulosic textile material and'curing the aminoplast thereon by maintaining ,the dried impregnated cellulosic material at about 205C. (preferably about 200C.) for about 1 30 minutes (preferably about 2 15 minutes). If desired, vacuum can be used to accelerate the curing step. Alternatively, curing can be produced by irradiating the dried impregnated cellulosic textile material with infrared, ultraviolet, X-ray s,'gamma rays, a proton beam, or an electron beam. The. improvement comprises incorporating into (i.e., admixing with) the ACA an effective amount (i.e., an effective quantity)'of a member selected from a first group consisting of;

carbon atoms, or -SO e. R, is hydrogen, an alkyl group having about 1-8 carbon atoms, -C1-l C1-l OH; or

f. R is hydrogen, an alkyl group having carbon atoms, CH CH OH;

g. A is a member, selected from a second group con the ACA, after admixing the first group member, containing about 2 50% (preferably about 30%) aminoplast based on the total weight of the ACA (i.e., original ACA plus first group member plus any solvent (water or non-aqueous solvent which is soluble in water) added with the first group member).

In the process of Embodiment F, supra:

1. x is 0; R is CH;;; and R R R and R are hydrogen.

2. x is 0; R is .-CH R is hydrogen; R is SO R is H; and R is H or -CH OH.

3. x is 0; R, is ---CH,, R R and R are hydrogen;

and R5 18 I In another preferred embodiment (Embodiment G") this invention is directed to an aqueous aminoplast composition (AAC) which is prepared by a process comprising; (a) forming a first mixture by admixing an aminoplast precursor in an amount to provide an effective amount of aminoplast in the final composition, aqueous formaldehyde (the formaldehyde is generally added as an aqueous solution analyzing about 20 50% HCHO; additional water can beadded if desired); and an effective amount (quantity) of a member selected from a first group consisting of;

ii. R is hydrogen or an alkyl grouphaving about 1-5 carbon atoms; i e

. iii. R is hydrogen or an alkyl group having about l-5 carbon atoms; v

iv. R is hydrogen, an alkyl group having about l-S carbon atoms, or SO{;

about 18 12 v. R, is hydrogen, an alkyl group having about l-8 carbon atoms, CH CH OH; or

:vi. R is hydrogen, an alkyl group having about l-8 carbon atoms, CH CH OH;

or CH OH; and vii. A is a member selected from a second group consisting of;

' CHI-cm /CHz-CH1 cur-01 n N CH); -N /O; and I CH2-CH2 CI-l CH Caz-cm sium carbonate and/or sodium carbonate, because of solubilities, neither barium hydroxide nor lithium hydroxide should be used where sodium carbonate and/or potassium carbonate are used); (c) forming a third mixture by maintaining the second mixture at about 40 90C. (preferably about C.) for about 30 240 minutes (preferably about 60 minutes); and

d) forming the AAC by adjusting the pH of the third mixture to about 6.5-7 (e.g., by adding an acid such as sulfuric acid, acetic acid, formic acid, hydrochloric acid, phosphoric acid, or the like). Typical of the aminoplast precursors which have been used with excellent results-to prepare this composition include melamine, urea, ethylene urea, dihydroxyethyleneurea,

' propyleneurea, and mixtures of two or more such aminoplast precursors.

ln preferred embodiments of the AAC set forth in Embodiment G, supra: v

' l. x is 0; R is CH;,; and R R R and R are hydrogen.

2; is 0; R, is CH;;; R is hydrogen; R is SO;,";

R is H; and R is H or CH OH. 3. x is'0', R is CH;,; R R and R are hydrogen;

' and R is CH OH. This invention is also directed to:

1. A composition consisting essentially of a cellulosic 3.'A composition consisting essentially of a cellulosic I ment H, supra:

l. x is R is -CH;,; and R R R and R are hydrogen. Y

2. x is 0; R is CH;,; R is hydrogen; R is SO;,; R, is H', and R is H or -CH OH. 3. x isQ; R is CH;,; R R and R are hydrogen; and R is -CH OH.

This invention is also directed to:

l. A composition consisting essentially of a cellulosic textile material wetted with about 60% of the AC A of Embodiment H, supra.

2. A composition consisting essentially of a cellulosic textile material wetted with about 10 60% of the ACA of Embodiment H, supra, and dried.

3. A composition consisting essentially of a cellulosic textile material wetted with about 10 60% of the ACA of Embodiment H, supra, dried, and cured, e.g., by heating or by irradiating.

In another preferred embodiment (Embodiment l) the process of Embodiment D, supra, and the embodiments thereunder has been conducted with excellent results using the AAC of Embodiment G, supra, and the embodiments thereunder.

In another preferred embodiment (Embodiment J) the process of Embodiment C, supra, and the embodiments thereunder has been conducted with excellent results using the ACA of Embodiment H,supra, and the embodiments thereunder.

In another preferred embodiment (Embodiment la) the process of Embodiment F, supra, and the embodiments thereunder has been conducted with excellent results using the ACA of Embodiment H, supra, and the embodiments thereunder.

We have found (Embodiment K) that the quality of paper (especially its wet strength, wet abrasion resistance, wet tensile strength, wet tear strength, and water absorption characteristics) can be greatly improved by impregnating the paper with an improved AAC of our invention, drying the impregnated paper, and curing the dried impregnated paper byirradiation or by heating. Where using an AAC for this purpose it is often called an aqueous aminoplast paper treating composition a terminology which we sometimes use.

We have also found (Embodiment L") that the quality of paper (especially its wet. strength, abrasion resistance, wet tensile strength, and wet tear strength) can be greatly improved by impregnatingthe paper with an improved ACA of our invention, drying the impregnated paper and curing the dried impregnated paper by heating the improved ACA containing about 0-1 5% of an acidic catalyst. Where using an ACA for this purpose it is often called an aqueous aminoplast paper treating agent a terminology which weoften use. I

We have also found (Embodiment M") that the general methods (or procedures) of Embodiment E. supra, and the embodiments thereunder can be used to improve the physical property of paper (especially its wet strength, wet abrasion resistance, wet tensile strength, and wet tear strength). Paper treated with the improved AACs and ACAs of our invention is useful as paper toweling, high wet strength absorbtive paper,

filler paper, and the like.

In another preferred embodiment (Embodiment N) this invention is directed to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast'composition comprising impregnating the cellulosic-textile material with the aqueous aminoplast composition and drying the impregnated cellulosic textile material, the improvement comprising incorporating into the aqueous aminoplast composition an effective amount of a member selected from a first group consisting of;

b. R, is hydrogen or'an alkyl group having about 1-5 carbon atoms; c. R is hydrogen or an alkyl group having about l5 carbon atoms;

d. R is hydrogen, an alkyl group having about 1-5 carbon atoms, or -SO e. R, is hydrogen, an alkyl group having about 1-8 carbon atoms, C-H CH OH; or t f. R, is hydrogen, an alkyl group having about l8 carbon atoms, CH CH OH;

In preferred embodiments of the process set forth in Embodiment N, supra:

1. x is R, is CH and R R R and R are hydrogen. i 2. x is 0; R is CH;,; R is hydrogen; R is -SO R is H; and R is H or CH OH. 3. x is O; R, is CH;;; R R and R are hydrogen; and R is -.-CH OH. In another preferred embodiment (Embodiment 0) this invention is directed'to an improvement in a process for treating a cellulosic textile material with an aqueous aminoplast creaseproofing agent, the process comprising impregnating the cellulosic textile material with the aqueous aminoplast creaseproofing agent and drying the impregnated cellulosic textile material, the

improvement comprising admixing the aqueous aminoplast creaseproofing agent with an effective amount of a member selected from a-first group consisting of;

f. R, is hydrogen, an alkyl group having about 1-8 carbon atoms, -C1-1 CH OH;

g. A is a member selected from a second group consisting of;

about 1-5 (i) CH2CH2 N on:

. cH,-om

(ii) Gin-on,

0 cm-cm and (111) CH1CH1 om-cn,

In preferred embodiments of the process of Embodiment 0, supra:

1. x is 0; R is CH;,; and R R R and R are 'drogen.

16 2. is O; R, is CH;,i R is hydrogen; R is SO R is H; and R is CH OH.

3. x is 0; R, is -CH R R and R, are hydrogen;

In another preferred embodiment (Embodiment P) this invention is directed to a process for treating a cellulosic textile material with a member of a later recited first group to' improve the physical properties of said cellulosic textile material comprising impregnating the cellulosic textile material with a sufficient quantity of an aqueous solution of a member selected from said first group to provide an effective amount of the first group member, said first group consisting of;

2 R1 2 i R1+ CH1 Ti IN ,rnid R1-.%--- CIH x |(IA 0 R5 R3 1r quantities where;

a. x is 0 or 1; y b. R is hydrogen or an alkyl group having about 1-5 carbon atoms; i f v c. R is hydrogen or an alkyl group having about l-S carbon atoms;

d. R is hydrogen, an alkyl group having about 1-5 carbon atoms, or SO{; r e. R is hydrogen, an alkyl group having about l-8 carbon atoms, -CH CH O1-l; or

f. R, is hydrogen, an alkyl group having about 1-8 carbon atoms, CH CH OH',-

or CH OH; and g. A is a member selected from a second group consisting of;

(i)' cm-cri,

IN cm cm-cm CH:CH1

N O cin oir,

and

(iii) m pin-cm cm-cit,

and drying the impregnated cellulosic textile matcrial. In preferred embodiments of the process of Embodiment P, supra: l. x is 0; R. is -CH;,; and R R R and R are hydrogen.

2. x is 0 R, is -CH R is hydrogen; R is S();, R, is H; and R is H or CH,, OH.

ii. R, is hydrogen or an alkyl group having aboutl-S carbon atoms; i

iii. R is hydrogen or an alkyl group having about l-5 carbon atoms;

iv. R is hydrogen, an alkylgroup having about l-5 I carbon atoms, or -SO3 v. R is hydrogen, an alkyl group having about vl-8 carbon atoms, CH CH OH, or

carbon atoms, -CH CH OH vi. R is hydrogen, an alkyl group having about l-8 vii. A is a member selected from a second group conthe equivalent ratio of aminoplast precursor to formaldehyde being about 1:1.1 2; (b) forming a second mixture by adjusting the pH of the first mixture to about 8.5-10.5; (0) forminga third mixture by maintaining the second mixture at about 40 90C. for

In another preferred embodiment (Embodiment R) this invention is directed to an improvement in a process for treating a cellulosic textile material'with an aminoplast creaseproofing agent comprising impregnating the cellulosic textile material with an aqueous aminoplast creaseproofing agent and drying the impregnated cellulosic textile material, the improvement comprising; preparingthe aqueous aminoplast creaseproofing agent by; (a) forming a first mixture by admixing an aminoplast precursor, aqueous formaldehyde, and an effective amount of a member selected from a group consisting of; 4

. 3. o R1 b--om "l :-N rand arc-{cu l li-A R5 R3 H where;

i. x is O or 1;

ii. R is hydrogen or an carbon atoms;

iii. R is hydrogen or' an alkyl group having about 1-5 carbon atoms;

iv R is hydrogen, an alkyl group having about 1 -5 1 carbon atoms, or .--SO{; v. R, is hydrogen, an alkyl group having about 1-8 carbon atoms, --CH CH OH; or

vi. R is hydrogeman'alkyl group having about l-8 carbon atoms, CH CH OH;

I or CH OH; and Y vii. A is a member selected from a second group consisting of;

M ciiz o'iii /cmcn. (rm-cu,

- /cin; N o; and N Gin-om CIIz-Cllz run-on,

the equivalent ratio of aminoplast precursor to formaldehyde being about 111.1 2; (b) forming a second about 30 240 minutes; and (d) forming the aqueous aminoplast composition by adjusting the pl-l of the third mixture to about 6.5-7.

In preferred embodiments of the process of Embodiment Q, supra:

1. x is 0; R is drogen.

2. x is 0; R is CH;,; R is hydrogen; R is SO{;

-Cl-l i and R R R and R are hy- R is H; and R is H or -CH OH.

-3. x is 0; R is 'CH R R and R arehydrogen; and R is CH OH.

mixture by adjusting the pH of the first mixture to about 85-105; (c) forming a third mixture by main-' taining the second mixture at about 40 90C. for about 30 240 minutes; (d) forming the aqueous aminoplast composition by adjusting the pH of the third mixture to about 65-7, and (e) admixing the aqueous aminoplast composition with an effective amount of an acidic curing catalyst.

in preferred embodiments of the process of Embodiment R, supra:

1. x is O; R, is --CH and R R R and R are hydrogen.

2. x is 0; R is CH R is hydrogen; R is -SO,,",

3. x is 0; R is CH R R and R are hydrogen; and R is -CH Ol-l.

alkyl group having about l-5 A Ev where;

a. x is or 1; b. R is hydrogen or an alkyl group having about 1-5 carbon atoms; 0. R is hydrogen or an alkyl group having about 1-5 carbon atoms;

d. R, is hydrogen, an alkyl group having about l-5 v carbon atoms, or SO;,; e. R is hydrogen, an alkyl group having about l-8 carbon atoms, -Cl-I CH OH; or

f. R, is hydrogen, an alkyl group having about 1-8 carbon atoms, CH CH OI-I;

or CH OH; and g. A is a member selected from a second group conand dryingthe impregnated cellulosic paper.

In preferred embodiments of the process of Embodiment S, supra:

1. x is O; R, is CH;,; and R R R and R are hydrogen.

2. x is O; R, is CI-I R is hydrogen; R is SO;,'; R is H; and R is H or CH OI-I.

3. x is 0; R is CI-I R R and R are hydrogen; and R5 iS CH2OH. I v In another preferred embodiment (Embodiment T) this invention is directed to an aqueous aminoplast nitrogen, argon, helium, or the like) introduced into composition (AAC) prepared by a process comprising;

(a) forming a first mixture by admixing an aminoplast precursor, water, ammonia, and an effective amount of a compound having the formula where;

i. x is O or 1; ii. R is hydrogen or an alkyl group having about 1 -5 carbon atoms; iii. R is hydrogen or an alkyl group having about 1-5 carbon atoms; iv. R is an alkyl group having about 15 carbon atoms, the mole ratio of said compound to ammonia being about 1:1 10 (preferably about 1:2 5); (b) forming a second mixture by maintaining the first mixture at about 20 100C. preferably about 4 6 hours); (c)

forming a third mixture by removing (e.g.) stripping or evaporating) unreacted ammonia from the second mixture (e.g., by boiling; or by the applicationof heat and reduced pressure to induce vigorous boiling; or by the application of heat while purging with an inert gas (e.g.,

the second mixture via a sparger); (d) forming a fourth mixture by admixing aqueous formaldehyde with the thirdmixture, the equivalent ratio of aminoplast precursor to formaldehyde in the fourth mixture being about 111.1 2 (preferably about 11125 1.75); (e) forming a fifth mixture by adjusting the pH of the fourth mixture to about 8.5-10.5; (f) forming a sixth mixture by maintaining the fifth mixture at about 25190C., preferably about -180C., (e.g., in a closed (pressurized) reaction zone) for about 0.25-4 hours (preferably about 1.5-3 hours); and (g) forming the aqueous aminoplast composition by adjusting the pH of the sixth mixture to about 6.5-7.

In another preferred embodiment this invention is directed to the AAC of Embodiment T, supra, in which x is 0; R and R are ,-CH and R is hydrogen.

In another preferred embodiment (Embodiment U) this invention is directed to an aqueous aminoplast creaseproofing agent (ACA) prepared by admixing the eofnpos ifion(AAL) ot Embodiment 1, supra, and an The ACA of Embodiment U (and the preferred embodiment thereunder) has been used with excellent results in the process of Embodiments J, Ja, R, and K.

Where an AAC is used to treat cellulosic paper it (the AAC) has been called an Aqueous Aminoplast Paper Treating Composition, and where an ACA is used to treatcellulosic paper it (the ACA) has been called an Aqueous Aminoplast Paper Treating Agent.v

DETAILED DESCRIPTION OF THE INVENTION There is an ever increasing demand for easy care, permanent press, creaseproof, and durable press garments and fabrics, that is, for garments and fabrics which have creases and pleats durably pressed into them and which remain substantially wrinkle-free in normal wear or use and which can be used after washing without requiring much, if any, repressing. These include theso-called wash-and-wear garments. As is well known, such durable press and permanent press garments and fabrics can be obtained by applying to and curing on the textile material one of more of a wide variety of heat curable aminoplasts (also known as curable durable press textile resins (U.S. Pat. No. 3,527,558, Tomasino, et al., 8/1 16.2)). These are aminoplasts which can be cured on the fabric by impregnating the fabric with an aqueous solution of the ami- In oneembodiment which is called precuring the drying and curing step is conducted as a continuous operation having the temperature in the drying stage below the curing temperature of the aminoplast. The drying stage is followed by a curing stage in which the dried impregnated fabric is heated to a temperature at which the aminoplast is cured, or the drying stage can be. followed by irradiation.

Aminoplasts (curable durable press and permanent press textile resins) excellently adapted for use in aminoplast creaseproofing agents and the preparation and use of these creaseproofing agents is well known to thoseskilled in the art. An aminoplast is generally applied to cellulosic textile materials as an aqueous aminoplast creaseproofing agent (ACA) comprising an aqueous solution or suspension. The aminoplast per se and the acidic catalyst component of the aminoplast creaseproofing agent are generally soluble in water but the ACA can also contain wetting'agents, softeners, brighteners, chelating agents, and the like, some of which can be only slightly soluble (or substantially insoluble) in water resulting in the presence of an insoluble phase being present in the ACA. In other words, the ACA is a dispersion when an insoluble phase is present.

In general the ACA is applied to a cellulosic textile material and dried (by the application of heat (maintaining the temperature below the curing temperature) and/or vacuum) to about the normal moisture content of the textile material under ordinary room conditions (e.g., ca. 1530C., and ca. 15-90% relative humidity). The thus dried textile material is then processed; (a) if the cellulosic textile material is fiber, it is spun and woven or formed into cloth or fabric, or formed into a non-woven cellulose containing fabric like material, pressed, and cured before or after being woven into thread or before or after being formed into cloth, fabric, ornon-woven cellulosic-containing fabric like ma terial. Alternatively, the dried fiber can be formed into a non-woven fabric and cured before or after being processed into a garment, sheet, tablecloth, or the like; (b) if thread, it is woven or formed into cloth or fabric, pressed and cured before or after being processed into a garment; and (c) if cloth or fabric, it can be (i) pressed free of wrinkles and cured; or (ii) processed into an article of clothing, pressed, and cured. Subsequent to curing the cloth or garment can be washed to remove any uncured aminoplast remaining thereon and other components of the aminoplast creaseproofing agent (e.g., catalyst) which are removable by washing. Alternatively, a garment can be impregnated with an aminoplast creaseproofing agent, dried, pressed, and cured.

We generally prefer to bleach and scour a cellulosic textile material before treating it with the ACA or AAC towhich we have added a member of the first group of the above Summary.

Typical aminoplasts 'which are used in aminoplast creaseproofing agents and/or typical acidic catalysts which are used in aminoplast creaseproofing agents to catalyze the curing of the aminoplast component of such agents, and typical methods of using aminoplast creaseproofing agents are taught by the following U.S. Pats. Nos. which are incorporated herein by reference:

2,974,432 (Warnock, et al., 38/144) 3,138,802 (Getchell, 2/243) 2,357,273 (Thurston, 260/29) 3,181,927 (Roth, eta1., 8/l16.3)

2,887,409 (van Loo, 117/1394) 3,450,485 (Reinhardt, et al., 8/1 16.3)

3,144,299 (Frick, et al., 8/1l6.3)

3,391,181 (Scheurel, 260/482) 3,527,558 (Tomassino, et al., 8/1 16.2)

3,531,806 (Shore, 2/243).

Preferred aminoplasts include diand poly-N- methyol, N-methoxymethyl, and N-lower alkoxymethyl derivatives of urea, cyclic ethylene urea, dimethylol alkyl, alkyltriazones, cyclic propylene urea, 4,5- dihydroxy cyclic ethylene urea, alkyl carbamates, triazines, uron, and thiourea. Preferred aminoplast also include di-methylol propylene urea; dimethylol ethylene urea; polymethylol melamine; formaldehydeimidazolidinone adducts; mixtures of dimethylol imidazolidinone-2 and its water-soluble ethers; methylol derivatives of 4,5-dihydroxyimidazolidone, 1,3-

, dimethyl-4,5-dihydroxy-2 imidazolidinone, and alkyl substituted 4,5-dihydroxy-2-imidazolidinones; reaction product of dimethylol dihydroxyethylene urea and pl ,3-dimethylol-4,5-bis(alkoxy)-2- imidazolidinones; l ,3-bis(hydroxymethyl )-2- imidazolidone; imidazolidinone-aminoplast blends; re-

.action products of urea, glyoxal and formaldehyde; polyalkylated monoureins; alkylated uron resin admixed with melamine formaldehyde compositions; N,N- dimethyloluron dialkyl ether and urea-formaldehyde compositions; alkylated uron resin and triazone compositions; amine-modified uron resins; N,N'- bis(acyloxymethyl) urons; N,N' bis(methoxymethyl) uron-formaldehyde addition products; N,N'-bis(methoxymethyl) uron-formaldehyde addition and reaction products; urea-formaldehyde condensation products; dicyandiamide-urea-formaldehyde agents; combination of monomeric and polymeric ureaformaldehyde condensates; 2-hydroxyethylamine-ureaformaldehyde condensation products; amine modified cyclic urea resins; polymethylol ureas having a high formaldehydezurea ratio, aminoethanol-ureaformaldehyde reaction product; highly alkylolated ni- I trogen compounds; and diketone dialdehyde-cyclic amide condensation products.

Aminoplast precursors are well known to those skilled in the art. Said precursors are amine type compounds (including amides) which can be reacted with formaldehyde in basic or slightly acidic systems to form a material which forms an aqueous aminoplast composition when the pH is adjusted to about neutral (e.g., to

' about 6.5-7). Among the many aminoplast precursors which have been used with excellent results are urea, biuret, melamine, and other triazines, ethylene urea, propylene urea, alkyl carbonates, thiourea, 4,5- dihydroxyimidazolidone, l,3-dimethyl-4,5-dihydroxy- 2-imidazolidone; alkyl substituted 4,5-dihydroxy-2- imidazolidinones; alkyl carbarnates; triazine resins; and the like.

Preferred acidic curing catalysts include zirconium acetate, aluminum acetate, lead acetate, manganese acetate, cupric acetate, zinc acetate, zinc nitrate, magnesium chloride, mixtures of zinc and aluminum nitrates, zinc fluoborate, zinc perchlorate, zinc chloride, magnesium chloride, mixtures of magnesium chloride and formic acid, mixtures of magnesium chloride and citric acid, sulfonic acid salts of ammonia, phosphoric acid salts of ammonia, volatile (e.g., gaseous) acids such as HCl, HBr, S and the like.

In another embodiment which is fully equivalent, an aqueous aminoplast composition (AAC), which can contain a brightener, a softener, a wetting agent, a chelating agent, and the like is prepared, but the acidic catalyst is omitted where preparing the AAC. Where using the AAC, :1 cellulosic textile material is impregnated with the AAC, dried, and cured by heating to the aminoplasts curing temperature in the presence of an acidic gas such as HCl, HBr, S0 or the like. Alternatively, the dried impregnated cellulosic textile material can be irradiated (e.g., with infrared, ultraviolet, X- rays, gamma rays, an electron beam, and the like) to cure the aminoplast. Excellent results have been obtained where an effective quantity of one or more of the aforesaid first group members was incorporated into the aqueous aminoplast composition before impregnating the cellulosic textile material with the aqueous aminoplast composition.

While the concentration of aminoplast and acidic catalyst in an ACA and the concentration of aminoplast in an AAC used in this invention are not critical, we generally prefer the aminoplast creaseproofing agent (solution or dispersion) asapplied to cellulosic textile material (i.e., the aminoplast plus water (and any water soluble solvent) plus first group member, plus (in the instant of an ACA) acidic curing catalyst, plus brighteners, softeners, chelating agents, and the like) to contain about 2.550% or higher (or about 5'30%) of said aminoplast and (in the instance of an ACA) about O.25l0% (or about 0.56%) of said acidic catalyst (acidic curing catalyst). As noted supra, the acidic catalyst can be omitted, thereby to form an aqueous aminoplast composition (AAC) rather than the ACA. The aminoplast of the aqueous aminoplast composition is cured by; (a) irradiating; or (b) heating in the presence of an acidic gas. An effective amount of aminoplast must be present in any ACA or AAC and an effective amount of acidic catalyst must be present in any ACA.

Typical of the wetting agents which can be used with excellent results are sodiumlauryl sulfate, dioctyl sodium 'sulfosuccinate, sodium lauroyl sarcosinate, alkyl phenolpolyoxyethylene glycols, sodium or potassium salts of high molecular weight alkyl sulfates, sodium or emulsions, acrylic emulsions, silicones, wax emulsions,

fluorocarbons, and chromium salts of higher fatty acids, sulfonated oils, sulfated fatty alcohols, quaternary ammonium salts, and the like.

The quantites of wetting agent, brightener, softener, and chelating agent are not critical to the instant invention; however, for economic reasons where one or more of these is used each is generally present in an effective amount. v

We can prepare the improved ACA described in our above Summary by admixing an effective quantity of a member of the aforesaid first group (the first group of the above Summary) and an ACA solution or dispersion. Where the first group member is a methylol compound having the formula (where x, R, R R and R areas recited in the above Summary) we can prepare the methylolv compound by reacting a compound (Compound A") having the formula (Compound A) with aqueous formaldehyde in the presence'of a base (e. g., Ba(OH) and adding the resulting methylol compound to the ACA. Alternatively, 'a methylol compound can be formed in situ by adding the Compound A to an ACA or to an AAC which contains excess HCHO. If the Compound A is added to an AAC the pH of the AAC should preferably be above 7 and preferably about 8.5-9.5; where forming the methylol compound in the AAC. (However, an acidic pH (e.g., generally about 5.0-6.9 or 5.5-6.5) is used where the aminoplast is dimethyloldihydroxyethyleneurea). Subsequent to forming the methylol compound in situ in an AAC containing excess formaldehyde, we can adjust the pH to about 6.5-7 (if pH adjustment is required) and add an acidic catalyst to convert the AAC to an ACA. Said ACA will, when formed, contain a methylol compound derived from Compound A.

We prepare the improved AAC of our Embodiment A, supra by admixing an effective quantity of a member selected from the first group recited in said Embodiment A and an AAC solution or dispersion. Where the first group member is a methylol compound having the formula ornon R3 (where x, R R R and R are as recited in said Embodiment A) we can prepare said methylol compound by reacting the above described Compound A with aqueous formaldehyde in the presence of a base and add the resulting methylol compound to the AAC. Alternatively, the methylol compound can be formed in situ by adding Compound A to an AAC which contains an excess of formaldehyde, thereby forming the composition recited in Embodiment A wherein the first group member is a methylol compound recited in said first group. i

We have found that the concentration of first group member present in the ACAs of our invention or the AACs of our invention can be varied over wide limits tion (the ACA or AAC as applied to a cellulosic textile material, i.e., the ACA or AAC plus said first group member (the first group of the Summary or Embodi ment H in the instance of an ACA and the first group of Embodiments A or G in the instance of an. AAC) plus any water (and other solvent) added with said first group member).

Excellent results have been obtained where said compositions contain concentrations of said first group member much higher than about 35%, but no technical advantage is obtained by using first group member concentrations greater than about 25% and the use of first group member concentrations higher than about 25% is economically unattractive. Said compositions in which the concentration of the first group member is significantly lower than the aforesaid about 0.5% produce beneficial results, but the hand, abrasion resistance, tensile strength,tear resistance, and shrinkage obtained at these low first group members concentrations are, in some instance, somewhat less desirable than where the first group members concentration is about 0.5% or higher. Because of our disclosure one skilled in the art can readily determine the concentration of said first group member which will give optimum results in a given ACA or AAC where said ACA or AAC is used for a particular purpose with a specific cellulosic textile material (e.g., to prepare wash-andwear or permanent press shirts from cotton cloth or from a blend of cotton and polyester).

N-methylollaetamide,

is a well knmown compound having been prepared by Einhom, et al., (Ann. 1908, 361, 113; Beilstein, 1921, 111,283; CA. 1908, 2, 2682) by reacting lactamide and formaldehyde solution in the presence of baryta (Ba- (OH The other N-methylol compounds recited in the first group of our above Summary and our above Preferred Embodiments can be prepared by the general method of Einhorn et al wherein lactamide is replaced by the appropriate amide having a hydrogen on the amide nitrogen. We prefer to prepare lactamide for use in our invention by the general procedure set forth infra.

We have found that incorporating one or more of our first group members into an ACA or AAC does not require any substantial change in the apparatus, or method, or conditions (temperature, time, and the like) used to apply the ACA or AAC to a cellulosic textile material and to dry and cure the aminoplast component'of the ACA or AAC where said ACA or AAC is applied to said textile material (or to eellulosic paper). In other words, the same general apparatus, method, and conditions used to apply a given ACA or AAC to a given cellulosic textile material (or to cellulosie paper) and to cure the aminoplast component of said ACA or AAC on said textile material (or paper) can be used to apply, dry, and cure said ACA or AAC afteran effective amount of one or more of our first group members has been admixed with said ACA or AAC (to' make the ACA or AAC- an improved ACA or AAC or our invention).

As is well known to those skilled in the art some aqueous aminoplast creaseproofing agents (AC A's) require the addition of an acid such as acetic acid, sulfuric acid, formic acid, phosphoric acid, or the like to reduce the'pl-l of the ACA before the ACA can be cured by the application of heat or heat and vacuum. Where using such an ACA in our invention, we add thereto a quantity of acid effective to render the ACA heat curable. This technique is well known in the prior art, and incorporating additives such as those of the above Summary or the above Embodiment l-l into an ACA does not significantly change the technique.

Claims directed to compositions and processes of the instant invention recite an effective amount (or an effective quantity) or a member of a first group (e.g., the first group of the above Summaryor the first group of Embodiment A, B, C, D, E, F, G, or H); however, because of our disclosure, it is readily apparent to those skilled in the art that an effective amount of first group members can be obtained by admixing two or more of the members of said first group even though the amount of any one individual group member in the re-. sulting mixture is not suffieient if taken alone to constitute an effective amount.

More than an effective amount of said group member (or a combination of more than 1 member of said group to total more than an effective amount) can be present in the compositions or processes of this invention, but, in general, little or no advantage is gained by using more than an effective amount, and cost of said group member (or members) tends to render the use of more than at least about an effective amount economi cally unattractive.

Claims directed to the compositions and processes of the instant invention recite an aqueous aminoplast composition, an aqueous aminoplast creaseproofing agent, an aqueous aminoplast paper treating composition, or an aqueous aminoplast paper treating agent; however, it will, because of our disclosure, be readily apparent to those skilled in the art that each of the aqueous aminoplast compositions or aqueous ami-v noplast agents can; (21) contain at least one aminoplast (i.e., each aqueous aminoplast composition or agent can contain 1, or 2, or more aminoplasts); and (b) each aqueous aminoplast composition can contain up to about 10-20% or more of a non-aqueous solvent (or a mixture of two or more non-aqueous solvents) said non-aqueous solvent (or solvents)-being soluble in water. Typical examples of non-aqueous solvents excellently adapted for inclusion in our aqueous compositions and agents are methyl alcohol, dimethylformamide, dimethyl sulfoxide, isopropyl alcohol, ethyl alcohol, and the like.

Likewise, because of our disclosure, it will be readily apparent to those skilled in the art that an aqueous solution of a memberof a first group" such as the aqueous solution of Embodiment E, supra, can contain up to about 20% or more of a non-aqueous solvent (or a mixture of two or.more' non-aqueous solvents) said non-aqueous solvent (solvents) being soluble in water. Typical examples of non-aqueous solvents excellently adapted for inclusion in an aqueous solution such as that of Embodiment E, supra, include ethyl alcohol, isopropyl alcohol, methyl alcohol, dimethyl sulfoxide dimethylformamide, and the like.

If desired, a cellulosic textile material can be impregnated with an ACA or AAC of our invention, dried, and placed in storage or shipped to a processing plant before being cured. Shelf life is generally at least about 3 months. Fabric which has been impregnated with an ACA or AAC and dried butnot cured can be rolled and shipped or stored as a fabric roll.

If desired, a cellulosic textile material can be impregnated with an aqueous system comprising a member of the first group of the above Summary, dried, and

placed in storage or shipped before being cured with an aldehyde. Shelf life is about 6 months. Fabric which has been impregnated with said group member and dried but not cured with aldehyde can be formed into a bolt or roll before being shipped or stored.

Itis well known to those skilled in the art that where one treats a cellulosic textile material with an ACA or an AAC he applies a quantity ofthe ACA or AAC sufficient to provide an effective amount (an effective quantity) of the aminoplast component of the ACA or AAC to the-cellulosic textile material. When using an ACA or an AAC of our invention we apply an amount sufficient to provide an effective amount of the aminoplast component of said ACA or AAC.

It is also well known to those skilled in the art that where one treats a cellulosic paper with an aqueous aminoplast paper treating agent or an aqueous aminoplast paper treating composition he applies a quantity of said agent or said composition sufficientto provide an effective amount (an effective quantity) of the aminoplast component (or components) of said agent or said composition to the cellulosic paper. Where using a paper treating agent or a paper treating composition of our invention we apply an amount sufficient to provide an effective amount of the aminoplast component of said agent or composition. i

As is well known in the art, where one cures a cellulosic textile material which has been impregnated with an AAC and dried by heating the dried impregnated cellulosic material in the presence of an acid (e.g., gaseous HCl, l-lBr, S0 formic acid vapor and the like) he has an effective amount of the acid present.

As is also well known in the art, where one cures a cellulosic paper which has been impregnated with an aqueous aminoplast paper treating composition and dried by heating the dried impregnated paper in the presence of an acid (e.g., gaseous HCl, l-lBr, S0 formic acid vapor, and the like) he has an effective amount of the acid present.

. The instant invention will be better understood by referring to the following specific but nonlimiting examples. It is understood that said invention is not limited by these examples which are offered merely as illustrations; it is also understood that modifications can be 'made without departing from the spirit and scope of the invention.

EXAMPLE 1 Lactamide was prepared from methyl lactate by the following procedure:

To l'mole of freshly distilled methyl lactate was added about 2 moles of ammonia. The ammonia was added as an aqueous solution analyzing about 28% NH The resulting mixturewas agitated for about 3 hours at about 20-30C. Then full vacuum from a water pump (aspiration type .filter pump) was applied to the mixture which was heated to about 70C. to remove water and unreacted ammonia. Purity of product was about 91% and ,conversion (one pass yield) was-about 97% of theory. The same general procedure was used to prepare amides of glycolic acid, ,B-hydroxypropionic acid, B-methoxypropionic acid, a-methoxypropionic acid, a-normal-butoxypropionic acid, methoxyacetic acid, ethoxyacetic acid, a-iso-propoxypropionic acid, and other organic acids of the type requiredto form the amides set forth in the above Summary. In each instance a high quality product was obtained in excellent yield.

Methyl a-methox-ypropionate (part of which was used to prepare the amide of a-methoxypropionic acid) was prepared by reacting methyl lactate with metallic sodium to form the sodium alkoxide which was converted to methyl a-methoxypropionate by reaction with methyl iodide Methyl bz-normal-butoxypropionate (part of which was used to prepare. the amide of a-normal-butoxyproionic acid) was prepared in a similar manner by replacing the methyl iodide with n-butyl iodide. Methyl B-methyoxypropionat'e (part of which was used to prepare the amide of B-methoxypropionic acid) was prepared in a similar manner from B-hydroxypropionate. Methyl ethoxyacetate (part of which was used to prepare the amide of ethoxyacetic acid) was prepared in a similar manner using methyl glycolate and ethyl iodidev as starting materials. Methyl oz-iso-propoxypropionate (part 'of which was used to v prepare the amide of a'-iso-propoxypropionic acid) was prepared in a similar manner from methyl lactate and iso-propyl iodide. Other methyl esters of alkoxy acids were prepared by the same general procedure.

EXAMPLE 2 The general procedure of Example 1 was used to prepare II II of excellent quality with excellent conversion by reacting methyl lactate with methylamine.

morpholine, where A was cnkcm v artwork and pyrrolidine, where A was l ll was obtained when the methylamme was replaced with C 2 -N methylethylamine.

CHr-CH:

0 1r CH3 JL Among the compounds of excellent quality prepared H CH OH in good to excellent conversion were those resulting 0 from the reaction of piperidine, morpholine, and pyrrolidine, respectively, with methyl lactate, methyl was obtained when the methylamine was replaced with B- Y YP P methyl g y t monoethanolamine, and

other-non E H mmkiFN 7 CH3 I crrlcocua,

on cmor-nqii i and was obtained when the-methylamine was replaced with o diethanolamme omcnlcrrz oom, respectively. Table I shows some of the substitued amides which I 4 were prepared by the above general method. 11

TABLE 1 lCsu-r Amine Substituted amide (CIImNII /on3 I (llhCllC-()CII3 CII3CII(J-N l l t) 0 CH3 om cm 3 omclnom ClIzOIIzCHa (tII;,(JIhCOCIh /NII CII2CIIzCN 0 cm 0011., 011; (ill:

0 C ll' Nllg o Ir ll ll r:monlcuc oom (2II3CHQ\CI[(IN 0 0 can (:m cm 0 armorial t mason; ll Cllq(|7lIC-O(;lh /NlI ClhClIC-N O CZIIJ C2115 CIIQCHaCHeCHg;

oornomomcm EXAMPLE 3 EXAMPLE 4 Compounds having the general formula o T 0 N/@ n on; R1 -CH; CA, l

l A 0- 1r 0 11 11 Whfiffl 1 2 X, and A are as defined in the'above was prepared by heating aniline with a large excess of I mary, were prepared by the general method of Example 2 except that the methylamine of Example 2 was replaced with; piperidine, where A was lactic acid for about an hour at about 105C. in a flask provided with a fractionating column for removing byproduct water, cooling the resulting reacted mixture and diluting it with a large volume of ice water to precipitate the anilide which was separated by filtration,

- washed with water, and air dried. An excellent product was obtained with a conversion in excess of about of theory where using a mole ratio ollactic acid to aniline of about 1011 and where the anilide was precipitated by pouring the cooled reacted mixture into a large volume of ice water (ca. 15 volumes of ice water per volume of reacted mixture).

The above general procedure was used to prepare anilides of a large number of hydroxy and alkoxy acids including anilidesof; a-methoxypropionic acid, a-ethoxypropinic acid, glycolic acid, methoxyglycolic acid, B-methoxypropionic acid, B-iso-propoxypropionic acid, and oz-hydroxybutyric acid. In each instance an anilide of excellent quality was obtained in excellent yield.

EXAMPLE aniline of Example 3 with diphenyl- Among the compounds prepared were those in which the lactic acid of the above procedure was replaced with the following acids; a-methoxypropionic acid; ,B-methoxypropionic acid; oz-n-butoxypropionic acid;

o a 0 1r Clla I 7 5O EXAMPLE 6 N-methylollactaniide of excellent quality was prepared by the procedure of Einhorn (Ann. 1908, 361,

l 13) which was referred to supra.

N-methylollactamide of excellent quality was also prepared by the following procedure:

20 Moles of lactamide (1886 g. of lactamide having a purity of about 94.4% was added to 3410 g. of aqueous formaldehyde solution (37% l-lCl-IO) in a stirred reactor at room temperature. The pH of the mixture was adjusted to 7 by adding an aqueous sodium hydroxide solution (20% NaOl-l); then25 g. of solid potassium carbonate was added bringing the pH of the resulting mixture to 10. Said resulting mixture was then heated to -70C. for 2 hours (with stirring) cooled to about 25C., and its pH was adjusted to 7 with sulfuric A large number of other N-methylolamides of excellent quality were prepared in good to excellent yields by the general procedure of Einhorn but modified by replacing the lactamide of Einhorn with another amide.

Table 11 lists some of the N-methylolamides prepared:

*In preparing this compound the Ba(OH) of Einhorn was replaced with NaOH. On acidification the "Na is replaced with H.

EXAMPLE 7 The sulfate ester,

ii (311311 C-N H:

i m- CHQCIIC-NHQ precipitated and was separated by filtration and recov ercd. The filtratewas poured into about 150 ml of dioxane. The bottom oil-like layer contained substantially all of the remaining where R R and x are as defined in the above Summary by replacing the lactonitrile with another nitrile having the formula where P, R and x are as above. Among the compounds formed were sour where R -R R R and x are as defined supra R being --SO is a sulfate ester of an amide of a hydroxy acid. The above ionic formula of said ester' negative valence is satisfied by a positive ion (or radical) other than hydrogen; e.g., Na*, K*, NH /2 Ca, or the like, (i.e., said sulfate ester is present as a salt). It is also readily apparent that such salt can hydrolyze 5 to give acidic or neutral reaction depending on the relative ionization constants of the acid form of said ester,

and the free base (e.g., KOH or NH OH) which can be derived from the aforesaid positive ion (or radical).

EXAMPLE 8 7 Four aqueous solutions were prepared; These were:

Solution A: An aqueous diemthyloldihydroxyethyleneurea (DMDHEU) solution having a 45% dissolved solid content. Said solution was prepared by reacting urea with glyoxal and methylolating the resulting product by reacting it with formaldehyde. Solution A had a free formaldehyde content of 7.1%. Solution B: An aqueous N-methylollactamide (NML) solution having a dissolved solid content of 72%. It was prepared from lactamide and formal- .dehyde.

Solution C: An aqueous zinc nitrate solution having a dissolved solid content of 50%.

Solution D: An aqueous lactamide solution having a dissolved solid content of 70%. I

A batch of ordinary ACA'(not an improved ACA of our invention) was prepared by. admixing an amount of Solution A to provide parts of solid and an amount of Solution C to provide 6 parts of tion 8B, supra) was prepared by admixing a quantity of Solution A to provide 7.5 parts of solid and an amount of Solution B to provide 5 parts of solid. To the resulting mixture 'was added an amount of Solution C to provide 1.5 parts of Zn(NO The resulting improve ACA was designated Solution 8C.

A batch of improved AAC (an AAC of our invention) was prepared by admixing an amount of Solution A to provide 30 parts of solid and an amount of Solution B to provide 20 parts of solid. The resulting improved AAC was designated Solution 8D. V

Another batch of improvedACA (an ACA of our in-' vention fully equivalent to th'e ACAs designated Solution 8B and Solution 8C, supra) was prepared by admixing an amount of Solution C to provide 1.5 parts of Zn(NO and one-fourth of the above described Solution 8D (i.e., to that quantity of Solution 8D which was Zn(N( The resulting ACA wasdesignated Soprepared from an amount of Solution A containing 7.5 parts of solid). The resulting ACA was designated Solution 8E."

8C, and 8D, supra) was prepared by adding a quantity I of Solution D to provide 6 parts of lactamide to onefourth of the above described Solution 8A. The resulting improved ACA was designated Solution 8F.

Each of the cured samples of cellulosic broadcloth was numbered with a number corresponding to the Run Number in which it was prepared. Thus, the sample from Run No. 98 became Sample 98, that from Run No. 9C became Sample 9C, etc.

EXAMPLE 10 Samples 9A and 9B'were submitted to'the tests listed in the following tables, and the results of these tests were as stated in said tables.

TABLE 4 Tear Strength Chlorine Damage 5 washings (Elmendorf) Flex Abrasion, Durable Press (Tensile) Sample Ratings, after Chlorinated Loss of No. Warp Fill Warp 5 washings Chlorinated 8L Scorched Tensile,

9A 272 1-60 55 3.8 29 I .29 0 9B 368 208 127 3 44 7 90 TABLE 5 Wrinkle Recovery Tensile Wrinkle Recovery After Washing 1 Inch Ravel Elongation Toughness Before Washing 5 Times Warp 70 Retention* Fill Warp ill Warp Fill Sample No. Dry Wet Dry Wet 9A 296 259 288 250 24 47 13 3.8 17.5 45.6 113.7 9B 288 241 2-76 256 I 34 67 4.4 19.5 74.8 247.5

'71 of tensile strength of the untreated fabric retained after treatment procedure was modified by replacing the, Solution 'D with 4.6 parts of water and 10.7 partsof cm cnoqvm.

a) l sont The resulting solution was designated Solution 80.

EXAMPLE 9 Run No. 9A: A sample (ca. 76 cm. by 38 cm.) of 110W broadcloth combed lawn .(a cellulosic broadcloth) was padded (ca. 81% wet pickup) with Solution 8A, described supra, after adjusting the dissolved solid content of said Solution 8A to 9% (by dilution with water). The padded sample was placed in a frame to maintain its size and shape, dried for 5 minutes at 93C., and then cured for 5 minutes at 163C. The cured sample was labeled Sample 9A.

Five additional runs were made using the general procedure described above but modified in each instance by replacing Solution 8A with the respective solution indicated in the following table, the dissolved solid content of each-solution being adjusted to the concentration indicated by dilution with water before padding the cloth sample with the'solution.

In this instance the general procedure of Run 9A was further modified by conducting the Curing step (5 minutes at 163C.) in an atmosphere of sulfur dioxide.

I Results substantially indistinguishable from those obtained with Sample 98 were obtained for Samples 9C, 9D, 9E, 9F, and 90, when said samples were submitted to the tests listed in Tables 4 and 5.

EXAMPLE 1 1 Run No. 11A: Several yards of cellulosic corduroy .cloth was padded with Solution 11A an aqueous dimethyloldihydroxyethylene urea solutionadjusted to The corduroy, which had taken up about 68.5% of its weight of the padding solution was dried at 93C. for 5 minutes. The thus dried corduroy was cut, pressed and cured (to simulate the fabrication of a garment from this material wherein it would be cut, sewed, pressed and cured). Pressing was carried out on a hot head press with a head temperature of 175C. It was steamed for 30 seconds, vacuumed for 30 seconds without the head and with the blower turned off, and baked at about 175C. 'for 15 seconds under pressure. It was then cured at 160C..for 5 minutes in an air circulating electric oven. A representative sample of the cellulosic corduroy cloth which had been treated according to 6'0 the procedure of Run No. 11A designated Sample Run No. 118: The general procedure of Run No. 11A was repeated but in this instance, the cellulosic corduroy cloth (from the same lot as that used on Run No. 11A) was padded with Solution 11B. Solution 11B, an improved ACA of our invention, was prepared by admixing an amount of Solution B (Example 8) with Solution 1 1A to provide 53 parts of Solution B solids in the resulting Solution 1 1B. A representative sample of the cellulosic corduroy cloth which had been treated according to the procedure of Run No. 1 1B was designated Sample 113."

The following table compares the results of tests made on Sample 11A and Sample 11B.

mixture rose to about 55C. The third mixture was heated to about 60C. and maintained at this tem- TABLE 6 perature for about 1 hour to form a fourth mixture. The fourth mixture was cooled to about 25C. and Wfinkle Rficovery Tensile its pH was adjusted to 7 2 by adding acid (ca 50% 1 t h R l 132,9 g i lfii, W aqueous H 50 to form a fifth mixture. The fifth mixture was filtered to remove a somewhat gummy w; 383 ii; 2% g: precipitate and the filtrate-an improved AAC .of 1 our invention-was admixed with 52 g. of t 7: of tensile strength of the untreated fabric retained after treatment. ZH(NO3)2 t0 fOl'm an ACAan improved Of TABLE 7 Tear Strength Durable Pressv Crease Retention Rating Sample (Elmendorf) Flex Abrasion. Ratings. after No. Warp Fill Warp washings lnitial After 5 washings 11A 1472 640 '386 4.3 v 5.0 5.0 I [B 2144 928 1133 4.5 5.0 5.0

EXAMPLE 12 our invention. This improved ACA was designated Run 12A: A conventional ACA was prepared by the Solution 12C Run No. 12D: A second improved ACA of our invenfollowing procedure.

' tion was prepared by the general procedure of Run No. A first mixture was prepared by admixing 152 g. of 30 water, 208.5 g. of ethyleneurea, and 492.5 g. of an aqueous formaldehyde solution (37% HCHO). The pH of the first mixture was adjusted to 7 by adding aqueous sodium hydroxide solution NaOH) to form a' second mixture. The temperature of the second mixture rose to about 40C., and a 6 g. portion of K CO was added thereto to form athird mixture having a pH of 9.9. The temperature of the third mixture rose to about 55C. The third mixture was heated to about 60C. and maintained at this temperature/for about 1 hour to form a fourth mixture. The fourth mixture was cooled to about C. and its pH was adjusted to 7.2 by adding acid (ca.

50% aqueous H SO to form a fifth mixture. Thefifth mixture was filtered to remove a somewhat gummy precipitate and the filtrate (a conventional AAC-not an improved ACC of our invention) was admixed with 52 g. of Zn(NO to form a conventional ACA--not an improved ACA of our invention. This conventional ACA was designated Solution 12A.

A first mixture was prepared by admixing 152 g. of I water, 108 g. of lactamide, 208.5 g. of ethyleneurea, and 492.5 g. of aqueous formaldehyde solution (37% HCHO). The pH of the first mixture was subjected to 7 by adding aqueous sodium hydroxide solution (20% NaOl-l) to form a second mixture. The temperature of the second mixture rose to about 40c., and a 6 g. portion of K CQ, was added thereto to form a third mixture having a pH of 9.9. The temperature of the third 11C; however, in this instance the procedure was modified by: (a) replacing the ethyleneurea with 238 g. of propyleneurea', (b) using 483 g. of the formaldehyde solution (c) using 106 g. of lactamide; and ((1) using 149 g. of water. The resulting ACA, an improved ACA of our invention, was designated Solution 11D.

EXAMPLE 13 Run No. 13A: A sample (ca. 76 cm. by 38 cm.) cotton sheeting was padded (ca. 81% wet pickup) with Solution 12A, described supra, after adjusting the dissolvedsolidcontent of said solution 12A to 9% (by dilution with water). The padded sample was placed in a frame to maintain its size and shape, dried for 5 minutes at 93C., and then cured for5 minutes at 163C. The cured sample was labeled Sample 13A.

Three additional runs were made using thegeneral procedure described above but modified in each instance by replacing Solution 12A with the respective solution indicated in the following table, the dissolved solid content of each solution being adjusted to the concentration indicated by dilution with water before padding the cloth sample with solution.

TABLE 8 Solid Content Run No. Solution No. of Padding Solution,

13B 12B 13.25 13C 12C 13.25 13D 12D 13.25 7 

1. IN A PROCESS FOR MANUFACTURING A GARMENT FROM A FABRIC PREPARED FROM A CELLULOSIC TEXTILE MATERIAL COMPRISING IMPREGNATING THE FABRIC WITH A HEAT CURABLE AQUEOUS ANINOPLAST CREASEPROOFING AGENT AND DRYING THE IMPREGNATED FABRIC AT A TEMPERATURE BELOW THE CURING TEMPERATURE OF THE AMINOPLAST COMPONENT OF THE HEAT CURABLE AMINOPLAST CREASEPROOFING AGENT ANDT THEN CUTTING SAID DRIED FABRIC TO THE SIZE, SHAPE AND STYLE OF THE DESIRED GARMENT, SEWING THE FABRIC TO PROVIDE GARMENT SEAMS, FINISHING THE CUT AND SEWN FABRIC TO MAKE A COMPLETED GARMENT THEREFROM, IMPARTING CREASES INTO THE COMPLETED GARMENT, AND THEREAFTER HEATING THE IMPREGNATED, DRIED, COMPLETED, AND CREASED GARMENT TO CURE THE AMINOPLAST AND TO INSOLUBILIZE IT IN SITU SO THAT THE COMPLETED GARMENT IS PRESSFREE AND THE IMPARTED CREASES THEREIN ARE UNAFFECTED AFTER REPEATED WASHING OF THE GARMENT, SAID HEAT CURABLE AMINOPLAST CREASEPROOFING AGENT CONSISTING ESSENTIALLY OF; (A) WATER; (B) AN AMINOPLAST; AND (C9 AN ACIDIC CATALYST, THE IMPROVEMENT COMPRISING ADMIXING THE HEAT CURABLE AQUEOUS AMINOPLAST CREASEPROOFING AGENT AND AN AMOUNT OF A MEMBER SELECTED FROM A FIST GROUP CONSISTING OF:
 2. The process of caim 1 in which x is 0; R1 is -CH3; and R2, R3, R4, and R5 are hydrogen.
 3. The process of claim 1 in which x is 0; R1 is -CH3; R2 is hydrogen; R3 is -SO3 ; R4 is H; and R5 is H or -CH2OH.
 4. The process of claim 1 in which x is 0; R1 is -CH3; R2, R3, and R4 are hydrogen; and R5 is -CH2OH.
 5. In a process for manufacturing a garment from a fabric prepared from a cellulosic textile material comprising impregnating the fabric with a heat curable aqueous aminoplast creaseproofing agent and drying the impregnated fabric at a temperature below the curing temperataure of the aminoplast component of the heat curable aminoplast creaseproofing agent and then cutting said dried fabric to the size, shape and style of the desired garment, sewing the fabric to provide garment seams, finishing the cut and sewn fabric to make a completed garment therefrom, imparting creases into the completed garment, and thereafter heating the impregnated, dried, completed, and creased garment to cure the aminoplast and to insolubilize it in situ so that the completed garment is pressfree and the imparted creases therein are unaffected after repeated washing of the garment, said heat curable aminoplast creaseproofing agent consisting essentially of; (1) water; (2) an aminoplast; and (3) an acidic catalyst, the improvement comprising admixing the heat curable aqueous aminoplast creaseproofing agent and 0.5-35% of a member selected from a first group consisting of;
 6. The process of claim 5 in which x is 0; R1 is -CH3; and R2; R3, R4, and R5 are hydrogen.
 7. The process of claim 5 in which x is 0; R1 is -CH3, R2 is hydrogen; R3 is -SO3; R4 is H; and R5 is H or -CH2OH.
 8. The process of claim 5 in which x is 0; R1 is -CH3, R2, R3, and R4 are hydrogen; and R5 is -CH2OH;
 9. The process of claim 5 in which the heat curable aminoplast creaseproofing agent and 2-10% of the first group member are admixed.
 10. The process of claim 9, in which the aminoplast is dimethylol dihydroxyethylene urea, dimethylol ethylene urea, dimethylol propylene urea, polymethylol melamine, a dimethylol alkyl carbamate, or a polymethylol triazine. 